Detergent composition



United States Patent DETERGENT COMPOSITION William C. York, deceased,late of Westbury, N.Y., by Ruth M. York, administratrix, Mineola, andLloyd I. Osipow, Monsey, N.Y., assignors to W. R. Grace & Co., acorporation of Connecticut No Drawing. Filed Oct. 27, 1958, Ser. No.769,571

14 Claims. (Cl. 252-137) In summary this invention is directed todetergent compositions comprising urea and a compound characterized bythe structural formula:

In the above formula, R is a hydrocarbon residue of the formula C Hwhere n is an integer of at least 7 and not more than 23 and m is aninteger in the range be tween 211-3 and 2n+l inclusive. Thus, R is analkyl, alkenyl or alkadienyl radical having from 7 to 23 carbon atoms.It is obvious that the product of the above formula is the same whetherthe acyl moiety is substituted on, the 6 or 6' position. Generically,the compounds are described as the mono fatty acid esters of diglucoseureide. Processes for their preparation are disclosed in our copendingapplication, SN. 663,580, filed June 5, 1957,

now US. Patent No. 2,993,445. Typical of such esters suitable for use inthe present invention include the caprylate pelargonate, caprate,undecanoate, laurate, tridecanoate, myristate, pentadecanoate,palmitate, margarate, stearate, nonadecanoate, arachidate,heneicosanoate, behenate, tricosanoate, lignocerate, oleate,palmitoleate, petroselinate, erucate, linoleate, eleosterate, and thelike. Suitable esters also include mixtures of those enumeratedhereabove. For example, the diglucose .ureide esters of coconut oil,palm oil, tall oil, olive oil, soybean oil and tung oil are alsooperative for purposes of the present invention. i

Theseesters are between diglucose ureide, and an ester of a fatty acidof the general formula: 1

the above. formula are suitable for the. alcoholysis reaction, sincethey result in the formation of an alcohol sufficiently volatile topermit its removal from the reaction mixture by simple distillation asthe reaction progrosses.

preparediby an alcoholysis reaction Since alcoholysis is an equilibriumreaction, it follows that some'diglucose nreide mono ester is formed2,981,691 Patented Apr. 25, 1961 whether or not the by-product alcoholis separated Thus, any organic ester of a fatty acid is suitable in the.

present process including those such as glycerides which are lessvolatile than the solvent selected for the reaction reaction willproceed only until equilibrium conditions are established. The reactionis shown below in Equation 1.

herea ture by using. reduced pressureto aid distillation of the 40alcohol thereform or by blowing an inert gas through or over the surfaceof the reaction mixture. Furthermore, a large surface. area will favorstripping of the product alcohol. A number of difierent types of filmevaporators are commercially available, and these can. be used withvacuum or an inert gas.

Suitable solvents for the alcoholysis reaction are those whichwilldissolve both diglucose ureide and the starting ester withoutpreferential reaction with either, of the products or the reactants.Preferably we use dimethylsulfoxide.

reaotion' is effectively catalyzed by an alkaline catalyst. By the. termalkaline catalyst we mean a basic organic salt. or a salt of a metalselected from groups I, ll orlVof the periodic table and aiwe ak, acid.Proton-accepting metals such as tin and zinc are also. ernbraced by theterm alkaline catalyst? Likewise, quaternary ammonium bases and similarcompounds. are at fective for this purpose. Exemplary catalysts includesodium hydroxide, potassium hydroxide, sodium carbonate, sodiummethoxide, potassium ethoxide,..trisodium phosphate, lithium hydroxide,magnesium hydroxide and lead oxide. Alkali metalhydroxides, alcoholates,c arbonates and phosphates are the preferred catalysts. Thecorresponding alkaline earth compounds are also suitable. 65 Thegeneralprocedure forpreparing the monofatty V esters of diglucose ureideis as follows: A quantity of in a container equipped with. a vacuumsealed stirrer and a c ns co m h s ti is an heatedrrtmedium. However, ifthe alcohol is not volatile, the

erably to a temperature of about 60-95 C. under a reduced pressure ofabout to 50 mm. Hg absolute for one hour to remove the major portion ofany moisture that may be present. A quantity. of catalyst (preferablymoisture free) is added to this solution and the temperature thereof ismaintained at about 60-95 C. under an absolute pressure of about 5-50mm. Hg. During the reaction some of the solvent is distilled ofi alongwith most of the by-product alcohol formed by the alcoholysis reaction.If desired, the reaction may be stopped at a convenient time to replacethe amount of solvent which has been distilled olf. With an efiicientfractionating column, the solvent will be returned automatically to thereaction mixture, thus obviating such a step.

While the time of the reaction is not particularly critical, we find itpreferable to let it continue from 1 to 12 hours. Actually, some productis formed in a few minutes at the preferred temperature range.' Therequired reaction time will depend upon the reaction temperature and theefliciency with which the product alcohol is stripped from the system.When the reaction is carried out under preferred conditions, e.g., withmethyl esters at 95% C. and potassium carbonate catalysts, from 1 to 5hours is generally adequate for complete conversion into the diglucoseureide ester.

After the reaction is stopped the catalyst can be neutralized with anyacid. Acetic acid is efiective for this purpose. sary feature inobtainingthe ester products, the purity of such products can be enhancedby converting the soap, which is" invariably formed in the reaction, tofatty acids by neutralization. The fatty acids are subsequentlyextracted from the reaction mixture using standard laboratorytechniques. Purification methods will be discussed in greater detailinfra.

The entire. reaction is preferably carried out under anhydrousconditions, since we have found that the .presence of several percent ofwater may result in reduced yields. cessively deleterious, ince moistureinitially present in such quantitiesisrapidly removed by distillation.In effect, the reaction is carried out under substantially anhydrousconditions.

The quantity of catalyst required to eflectively promotethe reaction isin the range of 0.050.30 mole per mole of starting ester. In thepreferred embodiment about 0.15 mole of catalyst are used. High levelsof catalyst produce excessive amounts of soap which in turn decreasesthe purity of the ultimate product. Using low levels, the. alcoholysisreaction is slowed considerably. V

The effective mole ratio of diglucose ureide to fatty acid ester forobtaining the ester compounds in good yield is generally about 3 to 1however, such a mole ratio is not absolutely critical and some degree ofvariation may be tolerated. If the mole ratio of diglucose A slightamount of moisture is not ex-.

isure of about 5 to 10 mm. Hg absolute represents a preferred range.However, a greater range of pressures of less than atmospheric isoperable.

The ester products are obtained from the solvent as crude crystallinemasses. They may be used as such or they may be further purified byvarious procedures readily apparent to those skilled in the art. On acommercial scale, several methods of purification are feasible. If thereaction is carried out using a substantial excess of diglucose ureide(to avoid formation of multi-substituted esters), the preferredpurification technique is as follows: At the completion of the reaction,the mixture is neutralized to convert soap to fatty acids. The solutionis then extracted with an aliphatic hydrocanbon solvent, such as hexaneor heptane, to remove free fatty acids and unreacted ester. Awater-immiscible solvent such as n-butanol is then added to thesolution, which is then solvent-extracted with an aqueous sodiumchloride solution to remove the reaction solvent, un-

While the neutralization step is not a necesureide to fatty acid esteris less than about 3 to l, more V of about -95 C. The volatility of thealcohol formed 'during the reaction is an important criterion forchoosing an operating temperature within the preferred'range.

- clients and furthermora'the interaction between theactive We havementioned that stripping alcohol from the system is facilitated using areduced pressure. We have-found, as a matter of practice, thata'reduc'ed pressuch an improved combination.

reacted diglucose ureide, and other water-soluble impurities. Thebutanol solution is then carbon treated to remove color, and distilled.A steam distillation will remove the last traces of butanol. If morehighly substituted esters of glucose ureide are present in the reactionmixture, the hexane treatment is preferably omitted. The reactionmixture is neutralized, partitioned between n-butanol and salt solution,washed further with salt solution, and the solvents removed bydistillation. The mono ester can then be recovered by precipitation fromany one of a number of polar sol vents, such as acetone or methanol.

A pure sample may be obtained conveniently by absorption chromatography.A chromatographic column may be prepared by packing a quantity of amixture containing 3 parts by weight Florex XXX (hydrated sodiumaluminum silicate of the fullers earth type) and 1 part by weight ofCelite 545 (diatomaceous earth) into a glass tube to give a longadsorbent column that is small in diameter. A portion of the sample tobe chromatographed is dissolved in a solvent mixture composed of equalparts of methanol and benzene. The column is pre-wetted with this samesolvent mixture and then the solution containing the sample is added tothe top of the column. After this solution has flowed below the toplevel of the column, fresh solvent is added and the column is elutedwith a quantity of the solvent mixture (benzene-methanol, 1:1).Fractions are collected at the bottom of the column and evaporated todryness. Usually, about 5 of the fractions collected contain the majorportion of the sample. The central fraction is generally considered tobe the purest of the 5 fractions;

this fraction may be characterized by determining its.

elsewhere in the specification.

The diglucose ureide monofat ty esters made by the V foregoing processare effective as cleaning agents per se, as mentioned in our copendingS.N. 663,580. The instant invention is based on our discovery that theseesters form combinations with urea to produce even better detergents.

'It is well known, of course, to combine a surface active agentpossessing good detergent properties with an alkali salt of a weakinorganic acid, a neutral inorganic salt, e.g., an alkali metal salt ofa strong inorganic acid, and a deflocculating agent to produce adetergent-composition. .However, the effectiveness of a particularcornposition depends upon balance between the above ingreagent and thebuilding materials. We have discovered The diglucoseureide mono-fattyester detergents, when'combined in proper portion with urea with orwithout additional building ma- .for the purposes of the presentinvention.

' positions are as follows.

fiproducts; preferably inia *finely divided solutiongof thedetergentcompositionis prcparedit teriails, form a truly superiordetergent composition which is astonishingly effective. both in hard.and soft Water. The basic composition may be varied to provide noveldetergent compositions effective for both light duty and heavy dutypurposes.

phosphate, trisodium orthophosphate andsodium h'xametaphosphate. Inpreparing our heavy duty detergent compositions we prefer to use asubstantial portion of sodium tripolyphosphate. For heavy dutydetergency the percentage of inorganic phosphates in the composition mayvary from about to 80%.. We find that the preferred-range is about2U60%. Alkali metal silicates also are effective as building materialsin addition to urea Suitable compounds Within this category includesodium silicate and sodium metasilicate pentahydrate. The silicates insolution undergo hydrolysis to give a pH of about 11.2.

In our compositions We may hav e from about ;52 5% of the alkali metalsilicate although the preferred quantity is from about 10-15%; A sodiumsalt of a strong inorganic acid is an important building material forour novel detergent compositions. Such a salt does: not hydrolyze but itdissociates to a sufficient extent to provide sodium ion in thedetergent solution. For a light duty detergent where a lws alkalinemedium is desiredwe find that sodium sulfate in quantities from about50-85% is desirable. rated in our novel heavy duty detergents. A smallquantity of an alkali metal carbonate such as sodium carbonate is alsodesirable as a building material. While the diglucose ureide monoesterstend tgact per se as dispersants or deflocculents, We haveronnd. that itis deconditions the ester comprises from about l530% by weightof thetotal con'1positionn The optimumamount of this active ingredientwillvary, aicc'ordingto the specific building materials, the contemplatedfield'of application, and the mannerof use. p

The urea is suitably used in a ratio. of 1-49 parts. of; l

urea per part of estenbwhether or not other builders .are,used.,Preferably the urea/ester ratio is l to 4:1. When other builders areused (in addition .to urea) they are suitaby used in a ratio of 0.5 to.2 parts of such builder (orbuilders, if morethan one additional builderis used to 1 part of combined ureaand est'er.

our novel com: Urea, .With..or"withou't other builders may be'added to.the ester to form a hot aqueous The general procedures for preparingslurry containing from about.40-60% solids concentration. Thismixtureisvi'gorously stirred to form a smooth and homogeneouspastel If1a slurry is. desired, the urea and any other additives may bedissolvedin a suitable I solvent and added to a slurry o-f'the monoester .The.urea and other builder's may also "be incorporated inttheyidetergentcomposition by a post treatment of driedfde tergent particles.s Thereafter these compos tions may be prepared in forms f solutionspastes, or"asxdry,pantially cond tion.

Phosphates which are suitable include, but are 5()% of this material isgenerally incorpo-' 6 be subjected to'suitable drying operations andconverted into particulate form. The mixture may be then spray dried,drum dried, or roll dried.

In order for a composition to be an excellent detergent, it must have(1) ability to wet and spread on liquid and solid surface, (2) abilityto form a stable foam, (3) ability to emulsify oily materials, (4)ability to peptize aggregates of solid particles, and (5) ability todedefiocculate or stabilize disperse systems of solid particles. Thediglucose ureide monoesters possess these characteristics to 'ameasurable extent. However, as an active agent in thedetergentcompositions described herein, these desirable properties ofthe esters are considerably enhanced. We have observed a tendency of thealkaline building material to cause saponification by a cleavage offatty esters within the detergent solutions during use. The soap thusformed is disposed of within the soil which is being removed by thedetergent. Builders by themselves are not particularly efiectiveemulsificants. The presence of the diglucose ureide esters and thesaponi- 'fication products resulting from chemical reaction within oftheir soaps on the surface of the material being treated.

All references to weight percents of compounds or solids employed referto weight percent of the compounds resulting after evaporation of thewater used (if any) during the detergent formation procedure.

Specific esters suitable for use in this invention may be prepared asset forth in the following Examples 1-7.

2 thati inayhavebeen present. A 7g. portion of potassium carbonate wasadded} The solution was then heated With stirring at C. forl2 hoursunderZa-pressureof 15 mm. Hg absolute. After the first 6 hours ofreaction, approximately 700m1. of distillate had been collected. A 700ml. portion of fresh dimethyl sulfoxide was added to the reactionmixture and distillation was continued for i i an additional 6 hours.

The solution wascooled, neutralized withia cetic acid and filtered i tofemove'fa small quantity of' diglucose ureide which precipitated duringthe cooling process. The 'clear filtrate, approximately 900 rnL, wasdihited with' 1 liter. 'of biitanol and 1 liter of concentrated salihesolution.

-- The -butanol layer was decolorized withactivated carbon and distilledto a thick residue. This residue was dissolved in 400 ml ;of hotethanol/ The solution was then i :"cooled and dilutedwith' 1 literofiacetone. The resultf 5 ing solution was chilled {to minus 10 C. to'precipitate .8. of product I 'fied was found to have a melting point of205-208 C.

' and a specific rotation of' J specification, supra. It melted at204-212 C. and had a specific rotation of Diglucose ureide myristate Theprocedure of Example I was substantially repeated using 81 gm. (0.33mole) of methyl myristate in lieu of a the methyl laurate. A 60 g. yieldof diglucose ureide myn'state was thereby obtained. After purificationby adsorption chromatography the residual product was found to have amelting point of 190-195 C. and a specific rotation of in dimethylsulfoxide. Upon analysis the following results were obtained: percent,carbon, theory 54.3, found 53.70; percent hydrogen, theory 8.4, found8.17; percent oxygen, theory 32.2, found 32.84; and percent nitrogen,

theory 4.7, found 4.99.

" EXAMPLE m Diglucose ureide palmitate I hada specific rotation of Itcontained 4.21% nitrogen (theory 4.5%) and 39f76% palmitic acidequivalent (41.0%) after purification by adsorption chromatography. Thenovel product thus purij in.i dimethyljlsulfoxide. Upon analysis iof thepurified Thepr'ocedure of Example I was substantially repeated using 'g.(0.33 mole) of methyl palmitate in lieu of .the methyl laurate. A 81 gm.yield of diglucose ureide "palmitate was thereby obtained. This crudematerial 8 EXAMPLE IV Diglucose ureide stearate The procedure of ExampleI was substantially repeated using g. (0.33 mole) of methyl stearate inlieu of methyl laurate. A 78 g. yield of diglucose ureide stearate wasthereby obtained. This crude material had a specific rotation of Itcontained 3.85% nitrogen (theory 4.33%) and 32.55% stearic acidequivalent (theory 43.6%). After purification by adsorptionchromatography the novel product was found to have a melting point of190-200 C. and a specific rotation of in dimethyl sulfoxide. Uponanalysis the following results were obtained: percent carbon, theory57.2, found 58.16; percent hydrogen, theory 8.93, found 9.11; percentoxygen, theory 29.5, found 29.27; and percent nitrogen, theory 4.32,found 4.03.

EXAMPLE V Diglm'ose ureide oleate The procedure of Example I wassubstantially repeated using 100 g. methyl oleate in lieu of methyllaurate. A

75 g. yield of diglucose ureide ole-ate was thereby obtained. This crudeproduct had a specific rotation of After purification by adsorptionchromatography the novel product was found to have a melting point of-170 C; and aspecific rotation of in dimethyl' sulfoxide. Upon analysisthe following re sults' are obtained: percent carbon, theory 57.40,found V 55.30; percent hydrogen, theory 8.64, found 8.42; percentoxygen, theory 29.63, found 25.83; and percent nitrogen,

. theory 4.32, found 4.69. 1

V EXAMPLE VI Diglucose ureide cocoate The procedure of Example I wassubstantially repeated using 81 g. (0.3 3 mole), of methyl cocoate inlieu of the 9 methyl laurate. A 42 g. yield of diglucose ureide cocoatewasv thereby obtained. The cocoate comprises methyl esters of coconutoil fatty acidcontainingabout 5.4 capryl ate', 8.4 caprate, 45.4laur'ate, '18 myristate, 10.5 palmitate, 2.3 stearate, 7.5 oleate, 0.8caproate, 0.4 arachidate,

product the following'l results are obtained: -p e rc ent;,car-- I Vbon, theoryi 56.0,:found 55.5; percent hydrogen, theory 8.7,found 8.43;percent oxygen, ,theory 30.9, found 31.68; qqre mm we t he and .41 1-the t r and 0.4% palrnitoleate. V EXAMPLE VI I' Diglucose 'ureidetallowate The procedure of Example I was substantially repeated, using100 g. methyl tallowate in lieu of methyl laurate. A 62 g. yield ofdiglucose ureide tallowate was thereby obtained., The tallowate. is amixture of fallow fatty acid.

- methyl esters containing about 6.3 myristate, 27.4 palmifate,

stearate, 49.6 oleate, and2.5% octadecadi-' 2,981,691 p 9 y 10 Thefollowing Examples VIII-XIX disclose procedures EXAMPLE XV for preparingthe novel urea-ester detergent compositions of this invention. Adetergent composition was prepared as per the procedure in Example XIVcontaining on a solids basis EXAMPLE 111 l about 20 parts diglucoseureide laurate, 40 parts sodium 7 tripolyphosphate, and 40 parts urea.The thus formed A detergent composition was prepared by forming adetergent composition exhibited excellent detersive propslurrycontaining about 20 parts diglucose ureide laurate ties on testing' 7 asprepared in Example I and 80 parts urea dispersed in about 67 parts ofWater. The slurry was agitated vigor- 10 EXAMPLE XVI ously at atemperature of about 60 C. to form a homogeneous mixture. It was thendried With heated air at a tem- A detergent WHIPOSIUOH Was p p red. bycharging 25 perature of about 120 C. The thus dried homogeneous Parts aur l laufate nd 75 Parts urea to a ball mixture was recovered as apowder which possessed ex- 111111 for d y mlllmg- After about 1 hour the110K10- cellent detersive properties in both hard and soft water.geneollsly ground dfi'fefgent composition 0 minus 60 mesh) wasdischarged. On testing, the thus formed detergent composition showedgood detersive properties. EXAMPLE IX EXAMPLE XVII Following theprocedure of Example VIII a powdered n homogeneous detergenteempesitionwae p p Following the procedure set forth in Example XVItaming 011 a Solids b about Parts diglllcose ureide a detergentcomposition containing parts diglucose tallowate asprepared in ExampleVII and 80 parts ureaureide tallowate and 75 parts urea was obtained. AThe thus formed detergent composltlonlpossessed good high grade ofdetersive properties resulted upon testing detersive and foamingproperties in both hard and soft 05 th f water. The resultant detergentis especially eifective for heavy duty; viz: treating, e.g., soiledcotton. EXAMPLE XVIII V t A detergent composition was prepared byforming a EXAMPLE X slurry containing 20 parts diglucose ureide laurateas prepared in Example I, 20 parts sodium tripolyphosphate, A mixture of20 parts diglucose ureide tallowate (pre- 20 parts urea, 40 parts sodiumsulfate, and about 67 pared in Example VII), 40 parts borax, and 40parts parts water. The slurry was agitated at a temperature urea washeated until the urea melted, stirred until sub of about 60 C. to insurehomogeneity for a period of stantially homogenous, then cooled'andpulverized. The about 30 minutes. The slurry was air dried at about 125C. Upon testing excellent detergent properties repowder was found to bea good detergent.

sulted from the thus formed detergent composition.

EXAMPLE XI EXAMPLE XIX Following the procedure in Example X a detergent40 composition was prepared comprising 20 parts diglucose A compositionfor use as a detergent containing on a ureide laurate as preparedby theprocedure in Example solids basis 2O parts diglucose ureide tallowate,20 parts I, 40 parts borax and 40 parts urea. The detergent propsodiumtripolyphosphate, 20 parts urea, and 40 parts erties of the thus formedcomposition were of high sodium sulfate was prepared by the procedure ofExamgrade. ple XVIII. The resultant detergent composition showed I alhih r d l f detersive ro erties.

EXAMPLE-XII' g gale" A detergent composition was prepared by forming anaqueous slurry containing on a solids basis 20 parts di- 53 glucoseureide tallowate, 40 parts borax, 40 parts urea, g V andabout 67 partsWater. The-slurrywasagitated at a l a temperature of about 70 C. to forma homogeneous z f w fl was F f i f i mixture for aboutl'hourandthereafter dried with heated e i 2 5 2 lg 3 a? 5 3 m air atatemperature of about 125 C. .Thje thus dried Ion W1 u 6 W1 or WI on 0 erers m e ergen Detergency evaluation mixture showed a-good grade ofdetersive properties. i systems Additionally comparison runs were madeto evaluate the urea-ester detergent composition withother t knowndetergent] builders. EXAMPLE XIII t A sample of Foster D. Snell (FDS)soiled cotton A detergent composition containing on-a solids basis aslelficted th e i n P? ge s T his 20. parts .diglucoseureide laurate,401 parts boraxfand40' t Sample pf p q; y t g d -fi e Indlan parts ureawas prepared by the procedure set out in Exd Cotton flq l .0 1 18 l i Fm l -4 ample The thus prepared detergent-composition carbon, 35.8%coconut oil, 17.9% coconut oil fatty acids hard andsoft water.

agitation for 30 Ir'ninutes 3 g the slurry was' elair dried p H 125The-thus formedw compositiondisplay exhibited a high grade of detersiveProperties-in both and 179% miileral on Suspended in Carbon tetrachlo" Iride.; The Indlan Head cotton fabric was dipped into I l the suspension,air-dried and rinsed lightly in water to j remove loosely adherent soil.It was again air-dried.

3 t p I Detergents were compared by running simultaneous Acompositionforvuse:asa detergentflwas preparedby wash-tests in astandard laboratory detergencytesting forming a slurry conta ningaboutyZOl'iazirts "diglujcose j; machine, e.g., Launderorneter. Thismachine rotates ureide gtallowatje', 40\ parts sodium;tripolyphosphate,4O ztwenty jars endover-end in a bath of fixed temperature.

partsnrea, andabouty67 part s w er. i 1 -,te r vigorous cellentdetersive prop ti es in both:

11 For check runs, the same series is repeated a second time and a thirdtime. The values for each detergent can be averaged and incidentalvariables will largely cancel out when the averages are compared. Such asystem is called a group experiment. The test conditions used are shownbelow in Table 1.

Reflectance reading By a standard reflectance meter, e.g., a Huntermultipurpose reflectometer set to read 100 on magnesia block.

Detergency data were obtained in both hard water of a hardnessequivalent to 15 U.S. grains and soft water of a hardness equivalent to2 U.S. grains. A U.S. grain of hardness is equivalent to 17.1 parts permillion of calcium carbonate.

The composition of the various built detergents tested is shown in Table2 along with the resulting reflectance gain of the soiled swatchessubsequent to a wash in the 12 Ultrawet K is a commercial grade ofsodiumalkylaryl sulfonate commonly used in built-detergent compositions.Buildings A and B are representative of commercial compositions. It willbe observed that when Ultrawet K is used with buildings A" and Bdetergency is panticularly good, while it is substantially poorer withbuildings C, D, E, and F, particularly at the lower concentration-0.2%.r Renex 30, a tridecyl alcohol-ethylene oxide condensate,

is considered to be one of the best nonionic detergents.

It will be observed'that it is relatively unaifected by the type ofbuilding.

Thediglucose ureide esters, on the other hand, are greatly influenced intheir performance by the type of building used. Maximum detergencyresults when urea is employed as the builder. This is important, becauseurea is considerably cheaper than the commonly used polyphosphates. Theeffect of urea in enhancing the detergency of the diglucose ureideesters appears to be unique, and is surprising in view of its ratherneutral effeet with other active agents.

In Table 3, urea, monoglucose ureide, diglucose ureide, and borax arecompared as builders, generally with or without sodium tripolyphosphate.The test conditions were the same as those used to obtain the results inTable 2 except that all tests were made in water having a hardness of 15U.S. grams.

TABLE 3 COTTON LAUNDEROMETER TEST RESULTS BRIGHTNESS UNITS GAINED G H II K L M N 0 Active a ent 20 2O 20 20 20 20 20 2O 20 Ur 80 40 40 Dor 8040 40 Sodium trlpoly 40 40 40 40 Monoglucose ur 80 40 Diglucose urei 8040 Built deter- Active agent gent conc.,

percent Diglucose ureide laurate 0. 2 7. 1 4. 5 8. 7 9. 3 6. 0 8. 6 i 7.B 7. 4 6, 7 0.35 10. 8, 10. 3 9. 9 11. 1 9. 7 17. 4 14v 2 14. 8 14. 5Diglucose ureide tallowate 0. 2 9. 3 2. 7 8. 7 9. 2 4. 4 9. 3 6. 6 8. 19.8 0. 13. 9 12.1 13. 6 14. 5 12. 8 22. 7 19. 0 20. 5 19. 7

different detergent compositions and a rinse. The weight percent (i.e.,0.2 and 0.35%) of built detergent composition added to the water iscomparable to amounts used in households and commercial launderm ats.

TABLE 2 0 tions used are shown below in Table 4.

' R TEST RESULTS BRIGHTNESS UNITS GAINED'AT 60 C. WITHO.2 AND 0.35 TooTToN LAuNDERoMETE BUILT DETERGENT I A B .0 D E F Active agen 25 25 2525 25 25 Sodium tripolyphosphate 40 Tetrasodium pyrophosphate 10 Bor'Sodium sulfate p 15 15 Sodium car n 75 Sodium metasilicate, pentahydrate10 10 N" silimitn 75 Ur 76 Water Active agent hardness, 0.35 0.2 0.350.2 0.35 0.2 0.35 0.2 0.35 0.2 0.35 02 r id'elaurate 2 5.5 8.2 6.1 11.55.4 4.1 7.8 4.9 14.9 16.6 Diglucoseu 2 2 7.6 8.7 5.9 12.3: 3.8 26 7.14.0. 18.5- 11.2

- Y 15 s a a: s1 1 allowate 2 .8 .6 j y I 9F. 15 5.6 10.1 5.5 9.1 4.23.0 2.7 14 11.9 11.7 UltrawetK -1 2 17.7 23.1 15.3 3.6 20.2 6.3 11.24.3' 5.6 1.8

Test Equipment Launder-Ometer palmitate, diglucose ureide oleate anddiglucose ureide myristate.

3. The detergent composition of claim 1 in which the ester is 20 to 50%by weight of combined ester and urea.

4. The detergent composition of claim 3 wherein the ester is a member ofthe group consisting of diglucose ureide laurate, diglucose ureidetallowate, diglucose ureide cocoate, diglucose ureide stearate,diglucose ureide palmitate, diglucose ureide oleate and diglucose ureideurements were made using a green filter.

Amount of solution per jar 100 ml.

Mechanical washing assistants.-- 8 rubber balls is diameter.

Temperature 60 C.

Speed of rotation of jars 40 RPM.

Time for washing..- 15 minutes.

Rinsing procedure" Rotate two minutes with 150 m1. of Water of samehardness as wash water.

Fabrics per ar Two swatches of FDS" soiled cotton 3 x 2 inches.

Reflectance reading By a standard reflectance meter, e.g.,

Hunter multipurpose rclectometer set to read 100 on magnesia block.

Following the rinse operation each swatch was placed between two papertowels and passed once through a wringer. The swatches were then driedat 65 i2 C. for a constant length of time to insure complete and equaldrying. The swatches were conditioned overnight at 50% relative humidityand two Hunter reflectance meas- Detergency measurements were made onFoster D. Snell soiled cotton (reflectance 22.0 for an unwashed swatch).A run was made toestablish a control on an unwashed FDS soiled cottonswatch in distilled water to set a basis from which the efiect of thedetergent compositions could be measured. Distilled water was also usedin all evaluation tests herein for making up detergent solutions, waterof varying hardness, for rinsing, etc.

In all runs soiled swatches were chosen so that they had an initialreflectance of 22.01-1 units. Tests were then made in a random order,with test swatches not being added to any given detergent solution untilit had reached the test temperature. Detergency tests were initiatedimmediately after addition of the swatches to the Launderometer. Afterthe washing, rinsing and drying were completed, reflectance measurementswere made as soon as possible thereafter to find the gain in reflectanceover the initial reflectance of 22.0:L-1 units. Theresults of thecomparative detergents are set forth in Table 5 below.

TABLE 5 Gain in reflectance units Built detergent No detergent-dis-0.20% 0.85%

tilled detergent detergent water only Control k 2.0 P 1 h 4.1 12.0 Q, i9. 9 9. 7 "All 4.7 6.2. Compositions (Weight percent) at time of test.

I Diglucose ureide laurate 25%, urea 75%. Diglucose ureide tallowate25%, urea 75%.

Sodium tripolyphosphate 37.7%, sodiumcarbonate 24.6%, sodium silicate(1:3.25) 8.3%, sodium carboxymethylcellulose 0.8%, nonionic surfactant(tail oil-ethylene oxide condensate) 15.6% and moisture 13.0%

I We claim: 1

1. A detergent composition consisting essentially of e urea and a monofatty acid ester of diglucose ureide wherein the acyl moiety attached tothe glucose group of the ester contains from 8 to 24 carbon atoms in a 1to 49:1 weight ratio respectively;

-2. The detergent composition of claim 1 wherein, the ester is a memberof the group consisting of diglucose ureide laurate, diglucose ureidetallowate, diglucose ureide cocoate, diglucose ureide stearate,diglucose ureide myristate.

5. A detergent composition consisting essentially of urea and a monofatty acid ester of diglucose ureide wherein the acyl moiety attached tothe glucose group of the ester contains from 8 to 2A carbon atoms in a 1to 49:1 weight ratio respectively and at least one member of the groupconsisting of 10-80% of an alkaline water soluble alkali phosphate, -85%sodium sulfate and up to 50% sodium tetraborate by weight, the balanceof said composition being the urea and ester.

6. A detergent composition consisting essentially of urea andamono fattyacid ester of diglucose ureide wherein the acyl moiety attached to theglucose group of the ester contains from 8 to 24 carbon atoms in a 1 to49: 1 weight ratio respectively and 10 to 50% sodium tripolyphosphateand 15-50% sodium sulfate by weight, the balance of said compositionbeing the urea and ester.

7. A detergent composition consisting essentially of urea and a monofatty acid ester of diglucose ureide wherein the acyl moiety attached tothe glucose group of the ester contains from 8 to 24 carbon atoms in a 1to 49: 1 Weight ratio respectively and at least one member of the groupconsisting of 10 to 80% sodium tripolyphosphate, 15-85% sodium sulfateand up to 50% sodium tetraborate by weight, the balance of saidcomposition being the urea and ester.

8. A detergent composition consisting. essentially of urea and a monofatty acid ester of diglucose ureide wherein the acyl moiety attached tothe glucose group of the ester contains from 8 to 24 carbon atoms and upthe urea and ester inwhich the ester is 20 to by weight of the combinedurea and ester.

9. A detergent composition comprising 20% diglucose ureide laurate, 40%urea and 40% sodium tetraborate by Weight.

10. A detergent composition comprising 20% diglucose ureide tallowate,40% urea, and 40% sodium tetraborate by weight.

11. A detergent composition comprising 20% diglucose ureide laurate, 40%urea, and 40% sodium tripolyphosphate by weight.

12. A detergent composition comprising 20% diglucose ureide tallowate,40% urea, and 40% sodium tripolyphosphate by weight.

13. A detergent composition comprising.20% diglucose ureide laurate, 20%urea, 20% sodium tripolyphosphate, and 40% sodium sulfate by weight.

14. A detergent composition comprisingv 20% diglucose ureide tallowate,20% urea, 20% sodium tripolyphosphate, and 40% sodium sulfate by weight.

References Cited in the file of this patent I UNITED STATES PATENTS 052,788,333 Goldsmith Mar. 13, 1955 2,814,612 Desty et a1. Nov. 26, 1951FOREIGNIPATENTS.

496,832 Canada Oct. 13, 1953 523,264- Belgium Oct. 31, 1953 to 50%sodium tetraborate by weight, the balance being

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF UREA AND MONO FATTYACID ESTER OF DIGLUCOSE UREIDE WHEREIN THE ACYL MOIETY ATTACHED TO THEGLUCOSE GROUP OF THE ESTER CONTAINS FROM 8 TO 24 CARBON ATOMS IN A 1 TO49:1 WEIGHT RATIO RESPECTIVELY.